Hardener composition for urethane resin

ABSTRACT

THIS INVENTION IS A HARDENER COMPOSITION FOR USE WITH URETHANE RESIN WHICH IS ODORLESS; EXHIBITS SUPERIOR WEATHERFASTENESS AND WORKABILITY; IS MANUFACTURE INDEXPENSIVELY; AND WHICH IS SUBSTANTIALLY FREE OF POISONOUS PROPERTIES.

United States Patent US. Cl. 252182 5 Claims ABSTRACT OF THE DISCLOSUREThis invention is a hardener composition for use with urethane resinwhich is odorless; exhibits superior weatherfastness and workability; ismanufactured inexpensively; and which is substantially free of poisonousproperties.

BACKGROUND OF THE INVENTION (1) Prior art This invention relates to asuperior hardener composition for use with urethane resin and providingsuperior workability and performance.

Among others, 4,4'-methylene*bis 2-chloroaniline (hereinafter referredto as MOCA throughout the present specification) having the followingformula:

is used most predominantly for the above service. The hardening agenthas superior performances for that purpose. However, it has a meltingpoint of 106 C., and is thus highly diflicult to handle. It is,therefore, a sincere desire of those skilled in the art, to provide animproved hardener having the superior solvent nature and performances asMOCA, yet being highly convenient in handling.

(2) Objects of the invention 'It is the main object of the invention toprovide an extender for use with urethane resin capable of satisfyingsubstantially the above desire and representing superiorweatherfastness, the least possible poisonous properties, odorlessness,which is colorless and which is cheap in its manufacturing cost.

Other objects of this invention will be apparent to those skilled in theart as the description of this invention proceeds.

DESCRIPTION OF THE INVENTION In order to satisfy the above object, thecomposit'on according to this invention comprises 204500 wt. parts of apropylated polycyclic aromatic hydrocarbon, having a boiling point of300450 C., a Gardner color index less than 10, a viscosity less than10,000 cps. at 25 C., a concentration of aromatic proton as measured bythe nuclear magnetic resonance absorption method of 15 80%, and a meannumber of substituted propyl groups per molecule of 1-4, or a partiallyhydrogenated hydrocarbon of the above kind, and about 100 wt. parts of4,4'-methylene-bis-2-chloroaniline.

The composition is of liquid to paste-like state, representing noappreciable deterioration even upon storage for a long period. When thehardener composition is used in combination with urethane resin, thehardened substance represents superior physical properties comparativeto those of MOCA. In addition, known defects of urethane resin, such asinferior water-proofness and weatherfastness can be highly improved. Theproducts can. be used in such industrial fields where heretofore coaltar and coal pitch have been used.

As was referred to hereinbefore, propylated polycyclic aromaticcompounds usable as the main component of the composition according tothe invention have boiling points ranging from 300 to 450 C., less than5% weight loss on heating as measured under the testing specificationJISK5400 prescribed in Japanese Industrial Standards, a Gardner colorindex of less than 10, and a viscosity less than 10,000 cps. at 25 C.These compounds are propylated polycyclic aromatics having 2-5 rings ofan aromatic proton concentration of 1580% as measured by thehigh-resolving NMR. The aromatic proton concentration can. be calculatedby the following Formula 1:

where,

H, is the total proton strength as measured by NMR- measurement.

H,, is the total proton concentration for the range of r(tau)-value of1.5-4 ppm. and taking the position of trimethyl silane as 10.

The number of propyl groups per mean molecular weight ranges from 1 to4.

The characteristics owned by the propylated polycyclic aromaticcompounds usable in the present invention have high mutual solubilitiesto both urethane resin and MOCA, thereby providing a high grade ofworkability and representing substantially no disadvantageous propertyto the compounded products. In addition, the color tone is rather whiteand there is substantially no appreciable limitation of coloring and nooccurrence of harmful and unhealthy odor, as may frequently be foundwith urethane/tar resins. In addition, superior water tightness is givento the compounded products which are cheaper in their manufacturing costthan conventional urethane resins.

In order to prepare the propylated polycyclic aromatic compounds asusable in the present invention, the origin of the starting material canbe found, for instance, in the ethylene bottom oil which may be obtainedas the residual from the ethylene or acetylene manufacturing plantwherein petroleum hydrocarbons such as crude petroleum oil, heavy oil,light oil and/or kerosene, naphtha, LPG and/ or the like are thermallydecomposed at 700l, 500 C., for a highly short period such as 5- 0.001second(s); oil tar and the like by-products produced in the hightemperature gasification of heavy oil or crude petroleum oil, and/orvarious residual oils rich in aromatic compounds and as obtained fromthe dealkylation process at high temperatures. The starting material is,as a first stage, subjected to hydrotreatment by contact with gaseoushydrogen, and then, as a second stage, to propylation by contact withpropylene, to the desired compound.

The purpose of the said first stage is to remove sulfur, nitrogenous,and metal components Which are liable to reduce or otherwise possiblyadversely effect the catalyzing function of the catalyst employed in thesecond stage, as Well as, to stabilize the reaction by saturation of theolefinic double bonds obtained by the result of the said thermaldecomposition. The first stage may be carried into effect in one or twosteps. Under proper conditions, one or two rings contained in thepolycyclic aromatic rings may be saturated. However, such saturationprovides no appreciable adverse effect so far as the thus modifiedproducts have specific physical properties as proposed by the invention.

denum, nickel or its mixture are used in sulfide, pure metal and/oroxide, being supported on conventional carriers such as alumina,diatomaceous earth (kieselguhr) or the like.

It will be seen that these reaction conditions are similar to thosewhich are conventionally employed in the petroleum refinery industry.

In the second stage for carrying out the propylation, the purpose issuch that by the propylation, the reaction products are converted tothose having higher boiling point and thus a lower viscosity. Inaddition, the heat resistant performance and the stabilization degreeagainst oxydation can be highly improved by said alkylation.

With less than unity of the number of propyl groups per mean molecularweight, the aforementioned advantageous characteristics could not beobtained. With more numerous propyl groups than 4, the alkylation canonly be realized under highly difiicult conditions and is thus toouneconomical to be adopted. The reaction conditions for the second stageare such as enumerated hereinbelow which are similar to those commonlyemployed in the as silica/ alumina; silica/magnesia; zeolite; solidphosphoric acid or phosphates or the like.

The thus obtained propylated oil is refiningly distilled to within theboiling range of 300-450 C., when convertingly based upon the normalpressure. In this way, the compounds functioning as the additiveaccording to the present invention can be obtained.

The additive thus obtained can be added in the range of 20-1, 500 wt.parts relative to 100 wt. parts of MOCA.

Use of less than 20 wt. parts will result only in a minor advantage fromthe point of cost reduction. Use of higher amounts than 1,500 wt. partsmay result in the invitation of an adverse effect upon the properties ofthe urethane resin.

The usable range of urethane resins is practically nonlimitating. Inconsidering the use of MOCA, the composition may be used ratheradvantageously in the form of sealants, waterproofing agents, seamlessfloor materials, paints and/or the like with highly advantageous meritsover the use of foam products.

The composition according to this invention can be used in combinationwith conventional coloring agents and/or fillers, and may be modified oradjusted by the use of conventional additives such as solvents or thelike.

MANUFACTURING EXAMPLE 1 Tarry substance obtained as by-products from theprocess for the manufacture of acetylene and ethylene by introducingSeria crude oil into superheated steam at 2,000

4 C., and heat-treating it at 1,350 C., for 0.003 second, washydrotreated and propylated under the conditions as enlisted in thefollowing Table I, and the reaction mixture was refiningly distilled toproduce a propylated polycyclic aromatic hydrocarbon A according to thisinvention.

TABLE I Hydro- Propylgen eno, Press, molecmolec- Temp., kg./ ular ularCatalyst cm. ratio ratio LHSV (Hydrotreatmont) cobalt-molybdenum]Alumina 350 35 5 0. 5 (Alkyl ion) silica/ alumina 200 20 3. 0 0. 5

The properties of the thus obtained hydrocarbon A are as follows:

TABLE II Boiling points, C 350-420 Viscosity, cps. (25 C.) 1,250Evaporative components, percent C., 3

hrs.) 0.4 Concentration of aromatic protons, percent 59.8 Number ofpropyl groups per mean molecular weight 2.0 Gardner color index 6MAUNFACTURING EXAMPLE 2 So-called ethylene bottom oil which had beenobtained in the manufacturing process of ethylene by thermaldecomposition of naphtha of Middle East Asia origin through the outerheating process, was hydrotreated and propylated by propylene and underthe treating conditions as enlisted in the following Table III. Then,the reaction mixture was refiningly distilled so as to produce apropylated polycyclic aromatic hydrocarbon B according to thisinvention.

TABLE III Hydro- Propylgen ene, Press, molecmolec- Temp., kg./ ular ularCatalyst C. om. ratio ratio LHSV (Hydrotreatment (1))NiS/alumina..-..... 40 5 0.5 (Hydrotreatment (2)) eobalt-molibdenum/umina 380 40 5 0. 5 (Propylation) silica/ alumina 200 20 3 0. 5

The thus obtained substance showed the following properties.

Example 1 Proplyated polycyclic aromatic hydrocarbons A and B which hadbeen prepared from the Manufacturing Examples 1 and 2 were addedsuccessively at a ratio of 1:1 with various hardening agents such asisocyanates, isocyanate prepolymers, amines, modified hardened oils andvarious polyols, so as to investigate their mutual solubility. As shownin the following Table V, these substances A and B showed completemutual solubility with them.

TABLE V NCO percent A B (1) Isocyanates and prepolymers:

(a) Isocyanate:

Toluene diisoeyanate (T.D.I.) 0.0. 0.0. Diphcnylmethane-4,4-diisocyanateS S Naphthalene-1,5-diisocyanate 0.0. 0.0. (b) Prepolymcr:

XL-1011 (manufactured by Takcda 3.3 0.0. 0.0.

Pharmaceutical 00., Osa a XL-ll7 (manufactured by 'Iakeda 3.3 0.0. 0.0

Pharmaceutical 00., Osaka). XL1025 (manufactured by 'Iakeda 3.5 0.0.0.0.

Pharmaceutical 00., Osaka). TP-309 (manufactured by Hitachi 3.5 0.0.0.0.

Reichfold). TP-352 (manufactured by Hitachi 3.5 0.0. 0.0.

Reichfold). TP-3l8 (manufactured by Hitachi 3.0 0.0. 0.0.

Reichfold SA-350 (manufactured by Hodogaya 3.0 0.0. 0.0-

Kagaku Kogyo K.K., Hodogaya). SA-400 (manufactured by Hodogaya 3.5 0.0.0.0.

Kagaky Kogyo K.K., Hodogaya). SA-50l (manufactured by Hodogaya 3.4 0.0.0.0

Kagaku Kogyo K.K., Hodogaya). Polyfiex-MT (manufactured by Dai 3.2 0.0.0.0.

ichi Kogyo Seiyaku K.K.). Sanpren-SEL-3 (manufactured by 3.6 0.0. 0.0.

Sanyo Kasei KKJ. UEX-504-SS (manufactured by Nip- 6.0 0.0. 0.0.

pon Elastomer K.K.). Adiprene L-100 (Du Pont) 6.4 0.0. 0.0- (2)Hardeners:

(a) Amine:

4,4-diamlnodiphenylmethane 0.0. 0.0- 4,4-methy1ene-bis-(2chloroaniline),0.0. 0.0.

MOCA. (b) Modified hardener:

Olester-0-1000 (manufactured by Mit- 0.0. 0.0-

sm' Toatsu Kogyo K.K.). Olester-0-1066 (manufactured by Mit- 0.0. 0.0

sui-Toatsu Kogyo K.K.). (c) Polyester type polyol:

Desmophen 800 (Bayer A.G.) P.S. P.5- Desmophen 1200 (Bayer A. G.) S. S.Desmophen 1700 (Bayer A.G.) S. S. (d) Polyether type polyol:

ADK-p-400 (manufactured by Asahi 0.0. 0.0.

Denka Kogyo K.K.). ADK-p-2000 (manufactured by Asahi 0.0. 0.0.

Denka Kogyo K.K.). ADKT300 (manufactured by Asahi 0.0. 0.0. ADK-T-700(manufactured by Asahi 0.0. 0.0.

Denka Kogyo K.K.).

No'rE.-Symbol 0.0. means full mutual solubility; RS. means full mutualsolubility and partial solution; S. means complete solution.

6 EXAMPLE 2 Propylated polycyclic aromatic hydrocarbon A obtained fromthe Manufacturing Example 1 were admixed in various ratios with 12.5parts of MOCA, and then with 100 parts of polyurethaneprepolymer(Adiprene-L-100) at 100 0., and cured by heating at 100 0.,for 2 hours to provide an elastomer. This elastomer was tested inaccordance with the testing specification prescribed under JIS-K6301(Japanese Industrial Standards). The results were shown in the followingTable VI.

For comparison, dibutyl phthalate (DBP), xyleneformalin resin (Nicanol)and coal tar (SS-tar for urethane use, manufactured by Osaka Yuki K.K.,Osaka) were used. With the first two, the resulted properties werehighly disadvantageous. With use of the coal tar, the products wereblack elastomers and unable to be colored as desired.

Next, the substances enlisted in the foregoing Table VI were immersedinto a pure water bath at 70 0., for 24 hours to test theirwater-proofness.

The results are listed in the following Table VII.

As clearly seen from Table VII, the composition proposed by the presentinvention provides superiorly improved water-proofness of the elastomer.

It has been further demonstrated that with no change of the materialurethane polymer, the hardness of the hard substances can be regulatedas desired which means a remarkable progress in the art.

TABLE VI Tensile Tearing Adiprene MOCA, MOCA/ strength, strength,Elongation, Hardness, L, parts parts A kgJemJ kg. cm. percent J IS,A-type Bleed 12. 5 353 63 930 91 None 12. 5 1/0. 25 355 64 935 0 Do. 12.5 1/1 310 1, 090 87 Do. 12. 5 1/2 273 56 l, 150 83 Do. 12. 5 1/4 200 451, 340 77 D0. 12. 5 1/8 141 37 1, 310 67 Do. 12.5 1/12 112 29 1,250 57D0. 12. 5 1/12 112 29 11, 250 57 D0. 12. 5 DBP 100 112 27 1,350 Do. 12.5 Nicanol 16 8 121 11 D0. 12. 5 Coal tar 100 1. 138 35 1,300 65 Do.

TABLE VII Tensile Tearing Adiprene MOCA, 40 CA/ strength, strength,Elongation, Hardness, L, parts parts "A" parts "A" kgJcmfl kgJcm.percent J IS, A-type Bleed 12. 5 326 58 860 91 None l/l 300 58 l, 050 87D0. 1/2 270 54 1, 100 83 Do. 1/4 200 43 1, 290 76 D0. 100 1/8 138 37 l,220 64 Do. Coal tar 100 128 34 1, 200 62 D0.

EXAMPLE 3 Propylated polycyclic aromatic hydrocarbon B according to thepresent invention was admixed with 100 wt. parts of urethane prepolymerXL-1025 (manufactured by Takeda Pharmaceutical Co. Ltd., Osaka); 9 wt.parts of MOCA and 50 wt. parts of calcium carbonate and the mixture wasleft alone for a week to harden. In this way, a sealant type urethanepolymer was obtained.

Several physical properties, test results on thermal resistance,water-proofness and anti-chemical property of the composition are shownin the following Table VIII.

As clearly demonstrated from the foregoing Table VIII, the sealant madeof the composition represents a superior performance.

It is claimed:

1. A hardener composition for use with a urethane resin, which comprisesfrom 20 to 1500 parts by weight of a propylated polycyclic aromatichydrocarbon, which exhibits a boiling point of from 300-450 C., aGardner color index of less than 10, a viscosity of less than 10,000cps. at 25 C., a concentration of aromatic proton as measured by thenuclear magnetic resonance absorption method of from l-80%, and the meannumber of substituted propyl groups per molecule being within a range offrom 1 to 4, or a partially hydrogenated hydrocarbon of theabove-identified kind, and 100 parts by weight of4,4'-methylene-bis-2-chloroaniline, said propylated polycyclic aromatichydrocarbon being prepared by a process which comprises:

(1) subjecting a member selected from the group consisting of ethylenebottom oil and oil tar to hydrotreating with gaseous hydrogen, and

(2) subsequently subjecting said hydrotreated ethylene bottom oil or oiltar to propylation by contacting the same with propylene,

said hydrotreatment step being carried out in the presence of a suitablecatalyst and at a temperature ranging from 40 to 450 C.; a pressureranging from 5 to 300 kc./cm. a hydrogen concentration ranging from 3 to15 mols; and a LHSV value ranging from 0.2 to 10.0; and

said propylation step being carried out in the presence of a suitablecatalyst and at a temperature ranging from 40 to 380 C.; a pressureranging from normal to kc./cm. a propylene concentration ranging from0.2 to 10.0 mols; and a LHSV value ranging from 0.2 to 10.0.

2. The composition of claim 1, wherein the catalyst employed during saidhydrotreating step is a member selected from the group consisting oftungsten, cobalt, molybdenum, and nickel, their sulfides, or theiroxides.

3. The composition of claim 2, wherein said catalyst is contained on aconventional catalytic support.

4. The composition of claim 3, wherein said support is a member selectedfrom the group consisting of alumina and diatomaceous earth.

5. The composition of claim 1, wherein the catalyst employed during saidpropylation step is a solid acid catalyst selected from the groupconsisting of silica-alumina, silica/magnesia, a zeolite, solidphosphoric acid, and a solid phosphate.

References Cited UNITED STATES PATENTS 8/1967 Mastin et a1. 26033.6 UB6/1968 Alexander et a1. 26018 TN US. Cl. X.R.

26025 A, 33.6 UB, 77.5 AM

